Nonwoven fabric

ABSTRACT

Disclosed is a nonwoven fabric formed from (i) a nonwoven fabric substrate and (ii) a fluorine-containing polymer adhering to the nonwoven fabric substrate, wherein the fluorine-containing polymer contains: 
     (a) repeating units formed from a fluorine-containing monomer which is alpha-chloro acrylate or alpha-chloro acrylamide containing a fluoroalkyl group, and
 
(b) repeating units formed from a halogenated olefin monomer, and
 
the fluorine-containing polymer is free from repeating units formed from a (meth)acrylate containing a linear or branched hydrocarbon group having at least 18 carbon atoms.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims benefit of Chinese Patent Application No.201610626325.X filed Aug. 2, 2016, incorporated herein by reference inits entirety.

TECHNICAL FIELD

The present invention relates to a nonwoven fabric, particularly anonwoven fabric to which a fluorine-containing polymer is adhered.

BACKGROUND ART

Hitherto, treatments of textiles with a fluorine-containing treatmentagent are proposed.

WO 2010/030044 discloses a treatment composition comprising afluorine-containing polymer having repeating units formed from afluorine-containing monomer, and a (meth)acrylate monomer containing acyclic hydrocarbon group. WO 2011/122442 discloses a treatmentcomposition comprising a fluorine-containing polymer having repeatingunits formed from alpha-chloro acrylate, and a (meth)acrylate monomercontaining a hydrocarbon group. These publications do not consider theapplication to a nonwoven fabric.

WO 2013/99611 discloses treatment of a nonwoven fabric with afluorine-containing treatment agent. However, sufficient water- andoil-repellency for the nonwoven fabric is not obtained.

SUMMARY OF THE INVENTION

One of objects of the present invention is to provide a nonwoven fabrichaving high water- and oil-repellency and high mechanical strength.

The present invention relates to the nonwoven fabric to which thefluorine-containing polymer adhered.

The present invention provides a nonwoven fabric comprising (i) anonwoven fabric substrate and (ii) a fluorine-containing polymeradhering to the nonwoven fabric substrate,

wherein the fluorine-containing polymer comprises:(a) repeating units formed from a fluorine-containing monomer which isalpha-chloro acrylate or alpha-chloro acrylamide containing afluoroalkyl group, and(b) repeating units formed from a halogenated olefin monomer, andthe fluorine-containing polymer is free from repeating units formed froma (meth)acrylate containing a linear or branched hydrocarbon grouphaving at least 18 (for example, at least 16, particularly at least 14)carbon atoms.

The fluorine-containing polymer gives high water repellency, oilrepellency, and/or soil resistance to the nonwoven fabric substrate.

Effect of the Invention

The nonwoven fabric of the present invention has excellent water- andoil-repellency, for example, excellent strong water-repellency and highwater pressure resistance, and excellent mechanical strength, forexample, high tensile strength.

MODES FOR CARRYING OUT THE INVENTION

In the present invention, the fluorine-containing polymer has adhered tothe nonwoven fabric. The nonwoven fabric to which thefluorine-containing polymer is adhered can be produced, for example byapplying a fluorine-containing treatment agent to a nonwoven fabricsubstrate (an untreated nonwoven fabric substrate).

The fluorine-containing treatment agent comprises thefluorine-containing polymer and a liquid medium.

(1) Fluorine-Containing Polymer

The fluorine-containing polymer comprises:

(a) repeating units formed from a fluorine-containing monomer which isalpha-chloro acrylate or alpha-chloro acrylamide containing afluoroalkyl group, and(b) repeating units formed from a halogenated olefin monomer.

The fluorine-containing polymer is free from repeating units formed froma (meth)acrylate, preferably a (meth)acrylate or (meth)acrylamide, whichcontains a linear or branched hydrocarbon group having at least 18carbon atoms.

(a) Fluorine-containing monomer

The fluorine-containing monomer (a) may be a compound represented by theformula:

CH₂═C(—Cl)—C(═O)—Y—Z—Rf

wherein Y is —O— or —NH—;Z is a direct bond or divalent organic group; andRf is a fluoroalkyl group having 1 to 20 carbon atoms.

The fluorine-containing monomer (a) is preferably a compound representedby the formula:

CH₂═C(—Cl)—C(═O)—Y—Z—Rf

wherein Y is —O— or —NH—;

Z is a direct bond,

a linear or branched aliphatic group having 1-20 carbon atoms(particularly an alkylene group), such as a group represented by theformula —(CH₂)_(x)— wherein x is 1 to 10,an aromatic group or cycloaliphatic group having 6-30 carbon atoms,a group represented by the formula —R²(R¹)N—SO₂— or the formula —R²(R¹)N—CO— wherein R¹ is an alkyl group having 1 to 10 carbon atoms andR² is a linear alkylene group or branched alkylene group having 1 to 10carbon atoms,a group represented by the formula —CH₂CH(OR³)CH₂—(Ar—O)_(p)— wherein R³is a hydrogen atom or an acyl group having 1 to 10 carbon atoms (forexample, formyl group or acetyl group), Ar is an arylene group (forexample, a phenylene group) optionally having a substituent group, and pis 0 or 1,a group represented by the formula —(CH₂)_(n)—Ar—(O)_(q)— wherein Ar isan arylene group optionally having a substituent group, n is 0 to 10,and q is 0 or 1, ora —(CH₂)_(m)—SO₂—(CH₂)_(n)— group or a —(CH₂)_(m)—S—(CH₂)_(n)— groupwherein m is 1-10, andn is 0-10, andRf is a linear or branched fluoroalkyl group having 1 to 20 carbonatoms.

In the fluorine-containing monomer, the Rf group is preferably aperfluoroalkyl group. The carbon number of the Rf group is preferablyfrom 1 to 12, for example, 1 to 6, particularly from 4 to 6, morepreferably 6. Examples of the Rf group include —CF₃, —CF₂CF₃,—CF₂CF₂CF₃, —CF(CF₃)₂, —CF₂CF₂CF₂CF₃, —CF₂CF(CF₃)₂, —C(CF₃)₃,—(CF₂)₄CF₃, —(CF₂)₂CF(CF₃)₂, —CF₂C(CF₃)₃, —CF(CF₃)CF₂CF₂CF₃, —(CF₂)₅CF₃,—(CF₂)₃CF(CF₃)₂, —(CF₂)₄CF(CF₃)₂ and —C₈F₁₇.

Preferably, the fluorine-containing monomer is an acrylate ester whereinthe Y group is —O—.

The Z group may be, specifically, a linear or branched aliphatic grouphaving 1-20 carbon atoms (for example, 1-10 carbon atoms, particularly1-4 carbon atoms, especially 1 or 2 carbon atoms) (for example, analkylene group), such as a group represented by the formula —(CH₂)_(x)—wherein x is 1 to 10,

an aromatic group or cycloaliphatic group having 6-18 carbon atoms,a group represented by the formula —R²(R¹)N—SO₂— or the formula —R²(R¹)N—CO— wherein R¹ is an alkyl group having 1 to 10 carbon atoms andR² is a linear alkylene group or branched alkylene group having 1 to 10carbon atoms, for example, by a —CH₂ CH₂ N(R¹)SO₂— group wherein R¹ isan alkyl group having 1 to 4 carbon atoms,a group represented by the formula —CH₂CH(OR³)CH₂—[Ar—(O)_(q)]_(p)—wherein R³ is a hydrogen atom or an acyl group having 1 to 10 carbonatoms (for example, formyl group or acetyl group), Ar is an arylenegroup (for example, a phenylene group) optionally having a substituentgroup, p is 0 or 1, and q is 0 or 1, a group represented by the formula—(CH₂)_(n)—Ar—(O)_(q)— (wherein Ar is an arylene group (for example,phenylene group) optionally having a substituent group, n is 0-10, and qis 0 or 1), ora —(CH₂)_(m)—SO₂—(CH₂)_(n)— group or a —(CH₂)_(m)—S—(CH₂)_(n)— groupwherein m is 1-10, and n is 0-10.

The aromatic group or the cycloaliphatic group may be substituted orunsubstituted. The S group or the SO₂ group may be directly bonded tothe Rf group.

Specific examples of the fluorine-containing monomer (a) include, butare not limited to, the followings:

CH₂═C(—Cl)—C(═O)—O—(CH₂)₂—Rf

CH₂═C(—Cl)—C(═O)—O—(CH₂)₄—Rf

CH₂═C(—Cl)—C(═O)—O—(CH₂)₂—S—Rf

CH₂═C(—Cl)—C(═O)—O—(CH₂)₂—S—(CH₂)₂—Rf

CH₂═C(—Cl)—C(═O)—O—(CH₂)₂—SO₂—Rf

CH₂═C(—Cl)—C(═O)—O—(CH₂)₂—SO₂—(CH₂)₂—Rf

CH₂═C(—Cl)—C(═O)—NH—(CH₂)₂—Rf

CH₂═C(—Cl)—C(═O)—O—(CH₂)₃—S—Rf

CH₂═C(—Cl)—C(═O)—O—(CH₂)₃—S—(CH₂)₂—Rf

CH₂═C(—Cl)—C(═O)—O—(CH₂)₃—SO₂—Rf

CH₂═C(—Cl)—C(═O)—O—(CH₂)₃—SO₂—(CH₂)₂—Rf

CH₂═C(—Cl)—C(═O)—O—CH₂CH₂N(CH₃)SO₂—Rf

CH₂═C(—Cl)—C(═O)—O—CH₂CH(OCOCH₃)CH₂—Rf

CH₂═C(—Cl)—C(═O)—O—CH₂-Ph-O—Rf (wherein Ph is 1,4-phenylene.)

CH₂═C(—Cl)—C(═O)—O—CH₂CH(OH)CH₂-Ph-O—Rf

CH₂═C(—Cl)—C(═O)—O—CH₂-Ph-Rf

CH₂═C(—Cl)—C(═O)—O—CH₂CH(OCOCH₃)CH₂-Ph-Rf

wherein Ph is a phenylene group, andRf is a fluoroalkyl group having 1-20 carbon atoms.

(b) Halogenated Olefin Monomer

Preferably, the halogenated olefin is free from a fluorine atom.

Preferably, the halogenated olefin is an olefin having 2-20 carbon atomsand substituted by 1-10 chlorine atoms, bromine atoms or iodine atoms.Preferably, the halogenated olefin is a chlorinated olefin having 2-20carbon atoms, particularly an olefin having 2-5 carbon atoms carbon andhaving 1-5 chlorine atoms. Preferable examples of the halogenated olefinare a vinyl halide such as vinyl chloride, vinyl bromide and vinyliodide, and a vinylidene halide such as vinylidene chloride, vinylidenebromide and vinylidene iodide. Vinyl chloride and vinylidene chlorideare preferred, and vinyl chloride is particularly preferred.

(c) Other Monomer

The other monomer (c) does contain a fluoroalkyl group. Preferably, theother monomer (c) other than the monomers (a) and (b) does not containfluorine. Examples of the other monomer (c) include (c1) a fluorine-freenon-crosslinkable monomer and (c2) a fluorine-free crosslikable monomer.

The other monomer (c) do not comprise the (meth)acrylate containing alinear or branched hydrocarbon group having at least 18 (for example, atleast 16, particularly at least 14) carbon atoms. That is, the presentinvention does not use the (meth)acrylate containing a linear orbranched hydrocarbon group having at least 18 (for example, at least 16,particularly at least 14) carbon atoms, for example, stearyl(meth)acrylate and behenyl (meth)acrylate.

(c1) Fluorine-Free Non-Crosslinkable Monomer

The fluorine-free non-crosslinkable monomer (c1) is a monomer which doesnot contain a fluorine atom. The fluorine-free non-crosslinkable monomer(c1) does not have a crosslinkable functional group. Unlike thecrosslinkable monomer (c2), the fluorine-free non-crosslinkable monomer(c1) has no crosslinkability. Preferably, the fluorine-freenon-crosslinkable monomer (c1) is a fluorine-free monomer having anethylenically unsaturated carbon-carbon double bond. The fluorine-freenon-crosslinkable monomer (c1) is preferably a vinyl monomer free fromfluorine. Generally, the fluorine-free non-crosslinkable monomer (c1) isa compound having one ethylenically unsaturated carbon-carbon doublebond.

The fluorine-free non-crosslinkable monomer (c1) may be:

(c1-i) a (meth)acrylate or (meth)acrylamide monomer containing a linearor branched hydrocarbon group having 17 or less carbon atoms, and/or(c1-ii) a (meth)acrylate or (meth)acrylamide monomer containing a cyclichydrocarbon group.

A preferable fluorine-free non-crosslinkable monomer, which includes the(meth)acrylate or (meth)acrylamide monomers (c1-i) and (c1-ii), is acompound represented by the formula:

CH₂═CA-T

wherein A is a hydrogen atom, a methyl group, or a halogen atom otherthan a fluorine atom (for example, a chlorine atom, a bromine atom, andan iodine atom), T is a hydrogen atom, an open-chain (linear orbranched) hydrocarbon group having 1 to 17 (for example, 2 to 15,particularly 3 to 14, especially 4 to 13) carbon atoms, a cyclic organicgroup having 4 to 30 carbon atoms, or an open-chain or cyclic organicgroup having 1 to 31 carbon atoms and an ester bond or amide bond.

In the (meth)acrylate or (meth)acrylamide monomer (c1-i), the T group isan open-chain group having 1 to 17 carbon atoms and an ester bond. Inthe (meth)acrylate or (meth)acrylamide monomer (c1-ii), the T group is acyclic organic group having 4 to 30 carbon atoms and an amide bond.

Examples of the cyclic hydrocarbon group having 4-30 carbon atoms are acycloaliphatic group having 4-30 carbon atoms, an aromatic hydrocarbongroup having 6-30 carbon atoms, and an araliphatic hydrocarbon grouphaving 7-30 carbon atoms.

Examples of the open-chain or cyclic organic group having 1-31 carbonatoms and an ester bond are: —C(═O)—O-Q and —O—C(═O)-Q wherein Q is aopen-chain (linear or branched) aliphatic hydrocarbon group having 1 to17 (for example, 2 to 15, particularly 3 to 14, especially 4 to 13)carbon atoms, a cyclic aliphatic group having 4-30 carbon atoms, anaromatic hydrocarbon group having 6-30 carbon atoms, or an araliphatichydrocarbon group having 7-30 carbon atoms.

Examples of the open-chain or cyclic organic group having 1-31 carbonatoms and an amide bond are: —C(═O)—NH-Q and —NH—C(═O)-Q wherein Q is aopen-chain (linear or branched) aliphatic hydrocarbon group having 1 to17 (for example, 2 to 15, particularly 3 to 14, especially 4 to 13)carbon atoms, a cyclic aliphatic group having 4-30 carbon atoms, anaromatic hydrocarbon group having 6-30 carbon atoms, or an araliphatichydrocarbon group having 7-30 carbon atoms.

Preferable Examples of the fluorine-free non-crosslinkable monomer (c1)include ethylene, vinyl acetate, acrylonitrile, styrene,polyethyleneglycol (meth)acrylate, polypropyleneglycol (meth)acrylate,methoxypolyethyleneglycol (meth)acrylate, methoxypolypropyleneglycol(meth)acrylate and vinyl alkyl ether. The fluorine-freenon-crosslinkable monomer (c1) is not limited to these examples.

The fluorine-free non-crosslinkable monomer (c1) may be a (meth)acrylateester or (meth)acrylamide containing an alkyl group. The number of thecarbon atoms in the alkyl group may be from 1 to 17, for example, from 2to 15 (e.g., from 3 to 14, particularly 4 to 13). The fluorine-freenon-crosslinkable monomer (c1) may be an acrylate represented by theformula:

CH₂═CA¹CO—Z¹-A²

wherein A¹ is a hydrogen atom, a methyl group, or a halogen atom (forexample, a chlorine atom, a bromine atom, and an iodine atom) other thana fluorine atom,

Z¹ is —O— or —NH—, and

A² is an alkyl group represented by C_(n)H_(2n+1) wherein n is 1 to 17.

Preferable examples ofA² include butyl and lauryl.

The fluorine-free non-crosslinkable monomer (c1) may be a (meth)acrylateor (meth)acrylamide monomer containing a cyclic hydrocarbon group.

The cyclic hydrocarbon group-containing (meth)acrylate ester monomer ispreferably a compound represented by the formula:

CH₂═CA²¹-C(═O)—O-A²²

wherein A²¹ is a hydrogen atom or a methyl group, andA²² is a cyclic hydrocarbon containing group having 4-30 carbon atoms.

The cyclic hydrocarbon group-containing (meth)acrylate ester monomer isa monomer having a high glass transition temperature (for example, atleast 50° C., particularly at least 80° C.) of a homopolymer thereof.

The cyclic hydrocarbon group-containing (meth)acrylate ester monomerdoes not have a fluoroalkyl group. The cyclic hydrocarbongroup-containing (meth)acrylate ester monomer may contain a fluorineatom, but preferably does not contain a fluorine atom.

A²¹ may be a hydrogen atom.

A²² is a cyclic hydrocarbon group which may have an open-chain group(for example, a linear or branched hydrocarbon group). Examples of thecyclic hydrocarbon group include a saturated or unsaturated, monocyclicgroup, polycyclic group or bridged ring group. The cyclic hydrocarbongroup is preferably a saturated group. The cyclic hydrocarbon grouppreferably has 4 to 30, more preferably 6 to 20 carbon atoms. Examplesof the cyclic hydrocarbon group include a cycloaliphatic group having 4to 20 carbon atoms, particularly 5 to 12 carbon atoms, an aromatic grouphaving 6 to 20 carbon atoms, and an araliphatic group having 7 to 20carbon atoms. The number of carbon atoms in the cyclic hydrocarbon groupis particularly preferably at most 15, for example, at most 12. Thecyclic hydrocarbon group is preferably a saturated cycloaliphatic group.Specific examples of the cyclic hydrocarbon group include a cyclohexylgroup, a t-butyl cyclohexyl group, an isobornyl group, a dicyclopentanylgroup and a dicyclopentenyl group and an adamantyl group.

Specific examples of the monomer containing cyclic hydrocarbon groupinclude cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate,benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl(meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl(meth)acrylate, tricyclopentanyl (meth)acrylate, adamantyl(meth)acrylate, 2-methyl-2-adamanthyl (meth)acrylate and2-ethyl-2-adamanthyl (meth)acrylate.

The presence of the cyclic hydrocarbon group-containing acrylate estermonomer gives higher water repellency and oil repellency imparted by thecopolymer.

(c2) Fluorine-Free Crosslinkable Monomer

The fluorine-containing polymer of the present invention may haverepeating units formed from the fluorine-free crosslinkable monomer(c2). The fluorine-free crosslinkable monomer is a monomer free from afluorine atom. The fluorine-free crosslinkable monomer (c2) has at leasttwo reactive groups and/or ethylenically unsaturated carbon-carbondouble bonds. The fluorine-free crosslinkable monomer (c2) may be acompound which has at least two ethylenically unsaturated carbon-carbondouble bonds or a compound which has at least one ethylenicallyunsaturated carbon-carbon double bond and at least one reactive group.Examples of the reactive group include a hydroxyl group, an epoxy group,a chloromethyl group, a blocked isocyanate group, an amino group and acarboxyl group. The fluorine-free crosslinkable monomer (c2) may be amono(meth)acrylate, di(meth)acrylate, or mono(meth)acrylamide containinga reactive group. Alternatively, the fluorine-free crosslinkable monomer(c2) may be di(meth)acrylate free from a reactive group.

Examples of the fluorine-free crosslinkable monomer (c2) include, butare not limited to, diacetone(meth)acrylamide, (meth)acrylamide,N-methylol(meth)acrylamide, hydroxymethyl (meth)acrylate, hydroxyethyl(meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate,2-acetoacetoxyethyl (meth)acrylate, butadiene, isoprene, chloroprene,glycidyl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, andneopentylglycol di(meth)acrylate.

When the fluorine-free non-crosslinkable monomer (c1) and/or thefluorine-free crosslinkable monomer (c2) are copolymerized, variousproperties such as water- and oil-repellency, stain-proofing properties,cleaning durability and washing durability of said properties,solubility in solvents, hardness and feeling may be improved dependingon the necessity.

Herein, “acrylate” or “acrylamide” includes not only a compoundcontaining a hydrogen atom at an alpha-position but also a compound inwhich the alpha position is substituted by another group (for example, amonovalent organic group including a methyl group, or a halogen atom).The term “(meth)acrylate” as used herein means an acrylate ormethacrylate, and the term “(meth)acrylamide” as used herein means anacrylamide or methacrylamide.

Each of the monomer (a), the monomer (b), and the monomer (c) (forexample, each of the monomer (c1) and the monomer (c2)) may be one aloneor a combination of at least two.

In the fluorine-containing polymer, the amount of the monomer (a) is 20%to 90% by weight, preferably 30% to 80% by weight, based on thefluorine-containing polymer.

In the fluorine-containing polymer, the amount of the halogenated olefinmonomer (b) may be 5 to 300 parts by weight, for example, 10 to 200parts by weight, particularly 20 to 100 parts by weight, especially 30to 80 parts by weight, and

the amount of other monomer (c) may be 0 to 800 parts by weight, forexample, 1 to 300 parts by weight, particularly 2 to 200 parts byweight, especially 3 to 100 parts by weight, based on 100 parts byweight of the fluorine-containing monomer (a).

In the fluorine-containing polymer, the amount of the fluorine-freenon-crosslinkable monomer (c1) may be 0 to 500 parts by weight, forexample, 1 to 300 parts by weight, particularly 2 to 200 parts byweight, especially 3 to 100 parts by weight, and

the amount of the fluorine-free crosslikable monomer (c2) may be 0 to 80parts by weight, for example, 0 to 50 parts by weight, particularly 0.1to 30 parts by weight, especially 1 to 20 parts by weight, based on 100parts by weight of the fluorine-containing monomer (a).

The amount of each of the fluorine-free non-crosslinkable monomers(c1-i) and (c1-ii) may be 0 to 500 parts by weight, for example, 1 to300 parts by weight, particularly 2 to 200 parts by weight, especially 3to 100 parts by weight, based on 100 parts by weight of thefluorine-containing monomer (a).

The number-average molecular weight (Mn) of the fluorine-containingpolymer may be 1,000 to 1,000,000, for example, from 5,000 to 500,000,particularly from 3,000 to 200,000. The number-average molecular weight(Mn) of the fluorine-containing polymer can be generally measured by GPC(gel permeation chromatography).

In the present invention, the monomers (a) to (c) are polymerized toobtain the fluorine-containing treatment agent (or the surface treatmentagent composition) wherein the fluorine-containing polymer is dispersedor dissolved in the liquid medium.

The monomer(s) may be polymerized in the presence of at least onecompound selected from the group consisting of a blocked isocyanatecompound and an organopolysiloxane compound. The amount of the blockedisocyanate compound (or the organopolysiloxane compound) may be 0 to 100parts by weight, for example, 1 to 50 parts by weight, based on 100parts by weight of monomers.

A fluorine-containing polymer containing a blocked isocyanate group isobtained by polymerizing the monomer in the presence of the blockedisocyanate compound. The blocked isocyanate compound is an isocyanateblocked by at least one blocking agent. Examples of the blocking agentinclude oximes, phenols, alcohols, mercaptans, amides, imides,imidazoles, ureas, amines, imines, pyrazoles, and active methylenecompounds. Other examples of the blocking agent include pyridinols,thiophenols, diketones, and esters. The blocked isocyanate compound maybe modified with a compound containing a hydrophilic group.

A fluorine-containing polymer containing a siloxane group is obtained bypolymerizing the monomer in the presence of an organopolysiloxanecompound (for example, a mercapto-functional organopolysiloxane and avinyl-functional organopolysiloxane). In one embodiment, themercapto-functional organopolysiloxane comprises siloxy units having theaverage formula:

(R₂SiO)_(a)(RR^(N)SiO)_(b)(RR^(S)SiO)_(c)

where; a is 0-4000, alternatively 0 to 1000, alternatively 0 to 400,b is 0-1000, alternatively 1 to 100, alternatively 1 to 50,c is 1-1000, alternatively 1 to 100, alternatively 1 to 50;R is independently a monovalent organic group,alternatively R is a hydrocarbon containing 1-30 carbon atoms,alternatively R is a monovalent alkyl group containing 1-12 carbons, oralternatively R is a methyl group;R^(N) is a monovalent amino-functional organic group,R^(S) each is a monovalent mercapto-functional organic group (R^(S)).

The amount of the fluorine-containing polymer (a solid content) may beabout 0.01 to 60% by weight, preferably about 0.1 to 40% by weight,particularly preferably about 5 to 35% by weight, based on thefluorine-containing treatment agent or the surface treatment agentcomposition.

Although the fluorine-containing polymer may be present in the form of asolution dissolved in an organic solvent, the fluorine-containingpolymer is preferably present in the form of an aqueous dispersion.

(2) Liquid Medium

The liquid medium may be an aqueous medium. The liquid medium may bewater alone, or a mixture of water and an (water-soluble) organicsolvent. The amount of the organic solvent may be at most 30% by weight,for example, at most 10% by weight (preferably at least 0.1%), based onthe liquid medium. The liquid medium is preferably water alone. Theliquid medium may be the organic solvent alone.

The amount of the liquid medium may be, for example, from 30 to 99.9% byweight, particularly 50 to 99% by weight, based on thefluorine-containing treatment agent (or the surface treatment agentcomposition).

(3) Surface Active Agent

The fluorine-containing treatment agent may contain a surface activeagent. In case that a fluorine-containing treatment agent contains anaqueous medium, the fluorine-containing treatment agent preferablycontains the surface active agent. The fluorine-containing treatmentagent preferably comprises the fluorine-containing polymer, the liquidmedium (preferably the aqueous medium), and the surface active agent.

In the present invention, the surface active agent may be at least oneselected from a nonionic surface active agent, a cationic surface activeagent, an anionic surface active agent, and an amphoteric surface activeagent.

Examples of the nonionic surface active agent include an ether, anester, an ester ether, an alkanolamide, a polyhydric alcohol and anamine oxide.

An example of the ether is a compound containing an oxyalkylene group(preferably a polyoxyethylene group).

An example of the ester is an ester from an alcohol and a fatty acid. Anexample of the alcohol is a monovalent-haxavalent (especiallydivalent-pentavalence) alcohol (for example, an aliphatic alcohol)having 1 to 50 carbon atoms (especially 3 to 30 carbon atoms). Anexample of the fatty acid is a saturated or unsaturated fatty acidhaving 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

An example of ester ether is a compound obtained by adding an alkyleneoxide (especially ethylene oxide) to an ester from an alcohol and afatty acid. An example of the alcohol is a monovalent-haxavalent(especially divalent-pentavalence) alcohol (for example, an aliphaticalcohol) having 1 to 50 carbon atoms (especially 3 to 30 carbon atoms).An example of the fatty acid is a saturated or unsaturated fatty acidhaving 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

An example of the alkanolamide is a compound formed from a fatty acidand an alkanolamine. The alkanolamide may be a monoalkanol amide or adialkanol amide. An example of the fatty acid is a saturated orunsaturated fatty acid having 2 to 50 carbon atoms, especially 5 to 30carbon atoms. The alkanolamine may be an alkanol having 2-50, especially5-30 carbon atoms which has 1-3 amino groups and 1-5 hydroxyl groups.

The polyhydric alcohol may be a dihydric to pentahydric alcohol having3-30 (or 10-50) carbon atoms.

The amine oxide may be an oxide (for example, having 5-50 carbon atoms)of an amine (a secondary amine or preferably a tertiary amine)

Preferably, the nonionic surface active agent is a nonionic surfaceactive agent containing an oxyalkylene group (preferably apolyoxyethylene group). Preferably, the carbon number of an alkylenegroup in the oxyalkylene group is from 2 to 10. Preferably, the numberof the oxyalkylene groups in a molecule of the nonionic surface activeagent is generally from 2 to 100.

Preferably, the nonionic surface active agent is a nonionic surfaceactive agent containing an oxyalkylene group and selected from the groupconsisting of an ether, an ester, an ester ether, an alkanolamide, apolyhydric alcohol and an amine oxide.

The nonionic surface active agent may include an alkylene oxide additionproduct of a linear and/or branched aliphatic (saturated and/orunsaturated) group, a polyalkylene glycol ester of linear and/orbranched (saturated and/or unsaturated) fatty acid, a polyoxyethylene(POE)/polyoxypropylene (POP) copolymer (a random copolymer or a blockcopolymer), and an alkylene oxide addition product of acetyleneglycol.Among them, preferable is one wherein a structure of an alkylene oxideaddition portion and a polyalkylene glycol portion are polyoxyethylene(POE), polyoxypropylene (POP), or a POE/POP copolymer (which may be arandom copolymer or may be a block copolymer).

Preferably, the nonionic surface active agent has a structure which doesnot have an aromatic group in view of environmental problems (such asbiodegradability and environmental hormone).

The nonionic surfactant may be a surfactant of the formula:

R¹O—(CH₂CH₂O)_(p)—(R²O)_(q)—R³

wherein R¹ is an alkyl group having 1 to 22 carbon atoms or an alkenylor acyl group having 2 to 22 carbon atoms,R² is independently, the same or different, an alkylene group having atleast 3 (for example, 3 to 10) carbon atoms,R³ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or analkenyl group having 2 to 22 carbon atoms,p is the number of at least 2, andq is 0 or the number of at least 1.

R¹ is preferably has 8 to 20 carbon atoms, especially 10 to 18 carbonatoms. Preferable examples of R¹ include a lauryl group, a tridecylgroup and an oleyl group.

Examples of R² are a propylene group and a butylene group.

In the nonionic surfactant, p may be the number of at least 3 (forexample, 5 to 200). q may be the number of at least 2 (for example, 5 to200). That is, —(R²O)_(q)— may form the polyoxyalkylene chain.

The nonionic surfactant is a polyoxyethylenealkylene alkyl ethercontaining a hydrophilic polyoxyethylene chain in the molecular centerand hydrophobic oxyalkylene chains (particularly, polyoxyalkylenechains). Examples of the hydrophobic oxyalkylene chain include anoxypropylene chain, an oxybutylene chain and a styrene chain. Amongthem, the oxypropylene chain is preferable.

A preferable nonionic surfactant is the formula:

R¹O—(CH₂CH₂O)_(p)—H

wherein R¹ and p are the same as the above.

Examples of the nonionic surfactant include the followings:

C₁₀H₂₁O—(CH₂CH₂O)_(p)—(C₃H₆O)_(q)—H

C₁₂H₂₅O—(CH₂CH₂O)_(p)—(C₃H₆O)_(q)—H

C₁₆H₃₁O—(C H₂CH₂O)_(p)—(C₃H₆O)_(q)—H

C₁₆H₃₃O—(CH₂CH₂O)_(p)—(C₃H₆O)_(q)—H

C₁₈H₃₅O—(CH₂CH₂O)_(p)—(C₃H₆O)_(q)—H

C₁₈H₃₇O—(CH₂CH₂O)_(p)—(C₃H₆O)_(q)—H

C₁₂H₂₅O—(CH₂CH₂O)_(p)—(C₃H₆O)_(q)—C₁₂H₂₅

C₁₆H₃₁O—(C H₂CH₂O)_(p)—(C₃H₆O)_(q)-C₁₆H₃₁

C₁₆H₃₃O—(CH₂CH₂O)_(p)—(C₃H₆O)_(q)-C₁₂H₂₅

iso-C₁₃H₂₇O—(CH₂CH₂H₂O)_(p)—(C₃H₆O)_(q)—H

C₁₀H₂₁COO—(CH₂CH₂O)_(p)—(C₃H₆O)_(q)—H

C₁₆H₃₃COO—(CH₂CH₂O)_(p)—(C₃H₆O)_(q)-C₁₂H₂₅

wherein p and q are the same as defined in the above.

Examples of the nonionic surfactant include a condensation product ofethylene oxide with, for example, hexyl phenol, isooctyl phenol,hexadecanol, oleic acid, alkane (C₁₂-C₁₆) thiol, a sorbitan mono-fattyacid (C₇-C₁₉) or an alkyl (C₁₂-C₁₈) amine.

The amount of the polyoxyethylene block may be 5 to 80% by weight, forexample, 30 to 75% by weight, especially 40 to 70% by weight, based onthe molecular weight of the nonionic surfactant (copolymer).

Generally, the average molecular weight of the nonionic surfactant isfrom 300 to 5,000, for example, from 500 to 3,000.

The nonionic surfactant can be used alone or in combination of at leasttwo.

Preferably, the nonionic surfactant is a combination of at least two. Inthe combination of at least two, at least one nonionic surfactant may bea compound represented by R¹O¹—(CH₂CH₂O)_(p)—(R²O)_(q)—R³ [especially,R¹O—(CH₂CH₂O)_(p)—H] wherein the R¹ group (and/or, the R³ group) is abranched alkyl group (for example, an isotridecyl group). The amount ofthe nonionic surfactant wherein the R¹ group is the branched alkyl groupmay be 5 to 100 parts by weight, for example, 8 to 50 parts by weight,especially 10 to 40 parts by weight, based on the total of 100 parts byweight of the nonionic surfactant. In the combination of at least two,the remaining nonionic surfactant may be a compound represented byR¹O—(CH₂CH₂O)_(p)—(R²O)_(q)—R³ [especially, R¹O—(CH₂CH₂O)_(p)—H] whereinthe R¹ group (and/or, the R³ group) is a (saturated and/or unsaturated)linear alkyl group (for example, a lauryl group (a n-lauryl group)).

Examples of the nonionic surface active agent include polyoxyethylenealkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fattyacid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fattyacid ester, polyoxyethylene sorbitol fatty acid ester, glycerol fattyacid ester, polyoxyethylene glycerol fatty acid ester, polyglycerolfatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine,polyoxyethylene fatty acid amide, fatty acid alkylol amide, alkylalkanolamide, acetyleneglycol, an oxyethylene addition product ofacetyleneglycol, a polyethylene glycol polypropylene glycol blockcopolymer. Polyoxyethylene alkyl ether and polyoxyethylene sorbitanfatty acid ester are preferable. Polyoxyethylene alkyl ether is morepreferable.

The cationic surface active agent may be an amine salt, a quarternaryammonium salt, and an oxyethylene addition-type ammonium salt. Althoughnot limited, specific examples of the cationic surface active agentparticularly include amine salt-type surface active agents, such as analkylamine salt, an amino alcohol fatty acid derivative, a polyaminefatty acid derivative, and imidazoline; and quarternary ammoniumsalt-type surface active agents, such as an alkyl trimethyl ammoniumsalt, a dialkyl dimethyl ammonium salt, an alkyl dimethyl benzylammonium salt, a pyridinium salt, an alkyl isoquinolinium salt andbenzethonium chloride.

A preferable example of the cationic surface active agent is:

R²¹—N⁺(—R²²)(—R²³)(—R²⁴)X⁻

wherein R²¹, R²², R²³ and R²⁴ are a hydrocarbon groups having 1 to 30carbon atoms, andX is an anionic group.

Specific examples of R²¹, R²², R²³ and R²⁴ are an alkyl group (forexample, a methyl group, a butyl group, a stearyl group, a palmitylgroup). Specific examples of X are halogen (for example, chlorine) andan acid (for example, hydrochloric acid and acetic acid).

The cationic surface active agent is particularly preferably amonoalkyltrimethyl ammonium salt (the carbon number of the alkyl is 4 to30).

Preferably, the cationic surfactant is an ammonium salt. The cationicsurfactant may be an ammonium salt of the formula:

R¹ _(p)—N⁺R² _(q)X⁻

wherein R¹ is a linear and/or branched aliphatic (saturated and/orunsaturated) group having at least 12 carbon atoms (for example,C₁₂-C₅₀),R² is H, an alkyl group having 1 to 4 carbon atoms, a benzyl group, or apolyoxyethylene group (the number of the oxyethylene groups is, forexample, at least 1 (particularly at least 2, especially at least 3) andup to 50) (CH₃ and C₂H₅ are particularly preferable),X is a halogen atom or a C₁-C₄ fatty-acid-salt group,p is 1 or 2,q is 2 or 3, andp+q=4.

The carbon number of R¹ may be from 12 to 50, for example, from 12 to30.

Specific examples of the cationic surfactant include dodecyl trimethylammonium acetate, trimethyl tetradecyl ammonium chloride, hexadecyltrimethyl ammonium bromide, trimethyl octadecyl ammonium chloride,(dodecylmethylbenzyl) trimethyl ammonium chloride, benzyl dodecyldimethyl ammonium chloride, methyl dodecyl di(hydropolyoxyethylene)ammonium chloride, benzyl dodecyl di(hydropolyoxyethylene) ammoniumchloride, N-[2-(diethylamino)ethyl]oleamide hydrochloride and dialkyl(hydrogenated beef tallow) dimethyl ammonium chloride. A cationicsurfactant having an ammonium chloride structure is preferable. Acationic surfactant having an ammonium chloride structure and having along-chain (for example, 10-30, particularly 14-24 carbon atoms)hydrocarbon group (particularly an alkyl group) such as octadecyl andhexadecyl is more preferable.

Specific examples of the anionic surfactant include sodium laurylsulfate, triethanolamine lauryl sulfate, sodium polyoxyethylene laurylether sulfate, sodium polyoxyethylene nonyl phenyl ether sulfate,triethanolamine polyoxyethylene lauryl ether sulfate, sodium cocoylsarcosinate, sodium N-cocoyl methyl taurine, sodium polyoxyethylenecocoalkyl ether sulfate, sodium diethylhexyl sulfosuccinate, sodiumα-olefin sulfonate, sodium lauryl phosphate, sodium polyoxyethylenelauryl ether phosphate, a perfluoroalkyl carboxylate salt (trade nameUnidyne DS-101 and 102 (manufactured by Daikin Industries, Ltd.)). Theanionic surface active agent is preferably a salt of an organic acid(for example, a salt of an organic acid with an inorganic base or anamine). More preferable is an alkyl sulfate ester salt, for example,ROSO₃ ⁻M⁺ wherein the carbon number of the alkyl group (R group) is, forexample, 8 to 30, and M is an alkali metal (for example, sodium orpotassium).

Examples of the amphoteric surfactant include amine oxides, alanines,imidazolinium betaines, amidobetaines, and betaine acetate. Specificexamples thereof include lauryl betaine, stearyl betaine, laurylcarboxymethyl hydroxyethyl imidazolinium betaine,lauryldimethylaminoacetic acid betaine, and fatty acidamidopropyldimethylaminoacetic acid betaine. Preferable are amineoxides, for example, R₃N═O wherein each R group is, for example, ahydrocarbon group (particularly an alkyl group) having 1-30 carbonatoms.

Each of the nonionic surface active agent, the cationic surface activeagent, the anionic surface active agent, and the amphoteric surfaceactive agent may be used alone or in a combination of at least two.

The fluorine-containing treatment agent may comprise an additive, inaddition to the fluorine-containing polymer, the liquid medium and thesurface active agent. Examples of the additive includesilicon-containing compounds, waxes and acrylic emulsions. Otherexamples of the additive include other fluorine-containing polymers,drying rate regulators, crosslinking agents, film formation aids,compatibilizers, surfactants, anti-freezing agents, viscosity modifiers,UV absorbers, antioxidants, pH adjusting agents, defoaming agents,texture regulating agents, slippage adjusting agents, antistatic agents,hydrophilizing agents, antimicrobial agents, antiseptics, insecticides,fragrances and flame retardants.

The polymer (the fluorine-containing polymer) in the present inventioncan be produced by any of conventional polymerization methods and thepolymerization condition can be optionally selected. The polymerizationmethod includes, for example, a solution polymerization, a suspensionpolymerization and an emulsion polymerization.

In a solution polymerization, there can be used a method of dissolvingthe monomer(s) into an organic solvent in the presence of apolymerization initiator, replacing the atmosphere by nitrogen, andstirring the mixture with heating at the temperature within the rangefrom 30° C. to 120° C. for 1 hour to 10 hours. Examples of thepolymerization initiator include azobisisobutyronitrile, benzoylperoxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide,t-butyl peroxypivalate and diisopropyl peroxydicarbonate. Thepolymerization initiator may be used in the amount within the range from0.01 to 20 parts by weight, for example, from 0.01 to 10 parts byweight, based on 100 parts by weight of total of the monomers.

The organic solvent is inert to the monomer, and dissolves the monomer,and examples of the organic solvent include an ester (for example, anester having 2-30 carbon atoms, specifically ethyl acetate and butylacetate), a ketone (for example, a ketone of 2-30 carbon atoms,specifically methyl ethyl ketone and diisobutyl ketone), and an alcohol(for example, an alcohol having 1-30 carbon atoms, specificallyisopropyl alcohol). Specific examples of the organic solvent includeacetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane,heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether,tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutylketone, diisobutyl ketone, ethyl acetate, butyl acetate,1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene,perchloroethylene, tetrachlorodifluoroethane andtrichlorotrifluoroethane. The organic solvent may be used in the amountwithin the range from 10 to 2,000 parts by weight, for example, from 50to 1,000 parts by weight, based on 100 parts by weight of total of themonomers.

In an emulsion polymerization, there can be used a method of emulsifyingmonomers in water in the presence of a polymerization initiator and anemulsifying agent, replacing the atmosphere by nitrogen, andpolymerizing with stirring, for example, at the temperature within therange from 50° C. to 80° C. for 1 hour to 10 hours. Examples of thepolymerization initiator include water-soluble initiators such asbenzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate,1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetylperoxide, azobisisobutylamidine dihydrochloride, azobisisobutyronitrile,sodium peroxide, potassium persulfate and ammonium persulfate; andoil-soluble initiators such as azobisisobutyronitrile, benzoyl peroxide,di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butylperoxypivalate and diisopropyl peroxydicarbonate. The polymerizationinitiator may be used in the amount within the range from 0.01 to 10parts by weight, based on 100 parts by weight of the monomers.

In order to obtain a polymer dispersion in water, which is superior instorage stability, it is preferable that the monomers are dispersed inwater by using an emulsifying device capable of applying a strongshearing energy (e.g., a high-pressure homogenizer and an ultrasonichomogenizer) and then polymerized. As the emulsifying agent, variousemulsifying agents such as an anionic emulsifying agent, a cationicemulsifying agent and a nonionic emulsifying agent can be used in theamount within the range from 0.5 to 20 parts by weight based on 100parts by weight of the monomers. The anionic emulsifying agent and/orthe cationic emulsifying agent and/or the nonionic emulsifying agent arepreferable. When the monomers are not completely compatibilized, acompatibilizing agent (e.g., a water-soluble organic solvent and alow-molecular weight monomer) capable of sufficiently compatibilizingthem is preferably added to these monomers. By the addition of thecompatibilizing agent, the emulsifiability and polymerizability can beimproved.

Examples of the water-soluble organic solvent include acetone, methylethyl ketone, ethyl acetate, propylene glycol, dipropylene glycolmonomethyl ether, dipropylene glycol, tripropylene glycol, and ethanol.The water-soluble organic solvent may be used in the amount within therange from 1 to 50 parts by weight, e.g., from 10 to 40 parts by weight,based on 100 parts by weight of water. Examples of the low-molecularweight monomer include methyl methacrylate, glycidyl methacrylate and2,2,2-trifluoroethyl methacrylate. The low-molecular weight monomer maybe used in the amount within the range from 1 to 50 parts by weight,e.g., from 10 to 40 parts by weight, based on 100 parts by weight oftotal of monomers.

A chain transfer agent may be used in the polymerization. The molecularweight of the polymer can be changed according to the amount of thechain transfer agent used. Examples of a chain transfer agent include amercaptan group-containing compound (especially alkyl mercaptan (forexample, having 1-30 carbon atoms)), such as lauryl mercaptan,thioglycol, and thioglycerol, and an inorganic salt such as sodiumhypophosphite and sodium hydrogen sulfite. The amount of the chaintransfer agent may be within the range from 0.01 to 10 parts by weight,for example, from 0.1 to 5 parts by weight, based on 100 parts by weightof total of the monomers.

The fluorine-containing treatment agent of the present invention may bein the form of a solution, an emulsion (particularly an aqueousdispersion) or an aerosol, but is preferably in the form of an aqueousdispersion. The surface treatment agent generally comprises thefluorine-containing polymer (active ingredient of the surface treatmentagent) and a medium (particularly a liquid medium, for example, anorganic solvent and/or water). The amount of the liquid medium may be 5to 99.9% by weight, particularly 10 to 80% by weight, based on thefluorine-containing treatment agent.

In the fluorine-containing treatment agent, the concentration of thefluorine-containing polymer may be 0.01 to 95% by weight, for example, 5to 50% by weight.

The surface treatment agent can be applied to a substrate to be treatedby a known procedure. Usually, the surface treatment agent is dilutedwith an organic solvent or water, is adhered to surfaces of thesubstrate by a well-known procedure such as an immersion coating, aspray coating and a foam coating, and is dried. If necessary, thetreatment liquid is applied together with a suitable crosslinking agent,followed by curing. It is also possible to add mothproofing agents,softeners, antimicrobial agents, flame retardants, antistatic agents,paint fixing agents, crease-proofing agents, etc. to the surfacetreatment agent. The concentration of the polymer in the treatmentliquid contacted with the substrate may be from 0.01 to 10% by weight(particularly for immersion coating), for example, from 0.05 to 10% byweight, based on the treatment liquid.

(4) Nonwoven Fabric Substrate

The nonwoven fabric of the present invention can be produced by applyingthe fluorine-containing treatment agent to the nonwoven fabricsubstrate. Generally, the nonwoven fabric substrate is an untreatednonwoven fabric, particularly a nonwoven fabric to which agents are notapplied.

Examples of fibers constituting the nonwoven fabric substrate includenatural fibers, synthetic fibers, semi-synthetic fibers, regeneratedfibers, and inorganic fibers. The fibers may be used alone or in acombination of at least two.

Examples of natural fibers include cellulosic fibers, such as cotton,flax and wood pulp; and chitin, chitosan, wool, and silk. Examples ofthe wood pulp include mechanical pulp such as ground wood pulp (GP),pressure ground wood pulp (PGW) and thermomechanical pulp (TMP);chemical pulp such as needle-leaf tree high-yield unbleached kraft pulp(HNKP; N material), needle-leaf tree bleached kraft pulp (NBKP; Nmaterial, NB material), broad-leaf tree unbleached kraft pulp (LUKP; Lmaterial) and broad-leaf tree bleached kraft pulp (LBKP, L material);recycled pulp such as deinked pulp (DIP) and waste pulp (WP); andsemi-chemical pulp (CP).

Examples of synthetic fibers include polyesters such as polyethyleneterephthalate, polybutylene terephthalate, polytrimethyleneterephthalate and copolyester; polyolefins such as linear low-densitypolyethylene, low-density polyethylene, high-density polyethylene andpolypropylene; polyamides such as nylon 6, nylon 66, nylon 610 and nylon46; acrylic fibers such as polyacrylonitrile; polyvinyl alcohol,polyurethane, and polyvinyl chloride.

Examples of semi-synthetic fibers include acetate and triacetate.

Examples of regenerated fibers include rayon, cupra, polynosic rayon,lyocell and tencel.

Examples of inorganic fibers include glass fibers and carbon fibers.

The fibers constituting the nonwoven fabric substrate is preferably acombination of natural fibers and synthetic fibers, for example, acombination of cellulosic fibers and polyester fibers, particularly acombination of wood pulp fibers and polyester fibers (for example,polyethylene terephthalate fibers). In the combination of natural fibersand synthetic fibers, the weight ratio of the natural fibers to thesynthetic fibers may be 5:95-95:5, for example, 30:70-70:30.Alternatively, in case that the intensity or durability is required ofthe nonwoven fabric, the weight ratio of the natural fiber to thesynthetic fiber may be 5:95-70:30, for example, 10:90-50:50, especially15:85-45:55.

The fluorine-containing polymer can be applied to the nonwoven fabricsubstrate by any of known methods of treating textiles with a liquid.The nonwoven fabric substrate may be dipped in the liquid (a liquid, forexample, a solution, or dispersion liquid comprising thefluorine-containing polymer), or the liquid may be adhered or sprayed onthe nonwoven fabric substrate. The treated nonwoven fabric substrate isdried and preferably heated at, for example, 100° C.-200° C., so as toexhibit water- and oil-repellency.

Alternatively, the fluorine-containing polymer may be applied to thenonwoven fabric substrate by a cleaning method, for example, may beapplied to the nonwoven fabric substrate in a laundry application or adry cleaning method.

The amount of the fluorine-containing polymer adhering to the nonwovenfabric substrate may be generally 0.001 to 20 parts by weight, forexample, 0.01 to 5 parts by weight, particularly 0.05 to 1 part byweight, based on 100 parts by weight of the nonwoven fabric substrate.

The term “treatment” means that the treatment agent is applied to thesubstrate by immersion, spray, coating or the like. The treatment givesthe result that the polymer which is an active component of thetreatment agent is penetrated into internal parts of the substrateand/or adhered to surfaces of the substrate.

EXAMPLES

The followings are examples which specifically explain the presentinvention. These examples are for the explanation of the presentinvention, but do not limit the present invention.

In the following Examples, parts, % and ratio are parts by weight, % byweight and weight ratio, unless otherwise specified.

The procedures of the tests were performed in the following manner.

Shower Water Repellency Test (Spray)

A shower water repellency test was conducted according to JIS-L-1092.The shower water repellency was expressed by water repellency No. (asshown in the below-described Table 1).

A glass funnel which has a volume of at least 250 mL and a spray nozzlewhich can spray 250 mL of water for 20-30 seconds are used. A test pieceflame is a metal flame having a diameter of 15 cm. Three sheets of atest piece having a size of about 20 cm×20 cm are prepared and the sheetis mounted on a test piece holding flame so that the sheet has nowrinkle. The center of the spray is located on the center of the sheet.Room temperature water (250 mL) is charged into the glass funnel andsprayed on the test piece sheet (for time of 25-30 seconds). The holdingflame is removed from a stand, one edge of the holding flame is graspedso that a front surface is downside and the other edge is lightly hitwith a stiff substance. The holding flame is further rotated 180° andthe same procedure is repeated to drop excess water droplets. The wettest piece is compared with a wet comparison standard to grade 0, 50,70, 80, 90 and 100 points in order of poor water-repellency to excellentwater repellency. The results are obtained from an average of threemeasurements.

TABLE 1 Water repellency No. State 100 No wet or water droplets adhesionon surface 90 No wet but small water droplets adhesion on surface 80Separate small water droplets-like wet on surface 70 Wet on half ofsurface and separate small wet which penetrates fabric 50 Wet on wholesurface 0 Wet on front and back whole surfaces

Water-Repellency Test (IPA)

The treated cloth is kept for at least 4 hours in a constant temperatureand humidity machine having a temperature of 21° C. and a humidity of65%. A test liquid (shown in Table 3) which has been also stored at 21°C. is used. The test is conducted in an air-conditioned room having atemperature of 21° C. and a humidity of 65%. A droplet of the testliquid in an amount of 0.05 mL is softly dropped by a micropipette onthe fabric. If the droplet remains on the fabric after standing for 30seconds, the test liquid passes the test. The water-repellency isexpressed by a point corresponding to a maximum content (% by volume) ofisopropyl alcohol (IPA) in the test liquid which passes the test. Thewater-repellency is evaluated as twelve levels which are Fail, 0, 1, 2,3, 4, 5, 6, 7, 8, 9 and 10 in order of a poor level to an excellentlevel.

TABLE 2 Water-repellency test liquid (% by volume) Point Isopropylalcohol Water 10 100 0 9 90 10 8 80 20 7 70 30 6 60 40 5 50 50 4 40 60 330 70 2 20 80 1 10 90 0 0 100 Fail Inferior to isopropyl alcohol 0/water100

IPR (Water Impact Penetration Resistance) Test

The IPR test was conducted according to AATCC Test Method 42-2000.

Water Pressure Resistance Test (Hydro Head)

According to an AATCC 127-2003 water pressure resistance test method, awater pressure resistance measuring apparatus was used to measure thewater pressure resistance.

Tensile Strength Test

A treated test fabric was cut to 15 cm×5 cm and pulled by a tensiletesting machine to measure a tensile strength in a lengthwise directionand a tensile strength in a transverse direction.

Preparative Example 1

CF₃CF₂—(CF₂CF₂)_(n)—CH₂CH₂OCOC(Cl)═CH₂ (n=2.0) (97.2 g), lauryl acrylate(73.66 g), pure water (405 g), aqueous glycol solvent (34.8 g),alkylamine oxide (11.75 g), and polyoxyethylene alkyl ether (6.17 g)were charged into a 1000 mL autoclave, and ultrasonicallyemulsification-dispersed at 60° C. for 15 minutes with stirring. Afterthe atmosphere in the autoclave was replaced with nitrogen, vinylchloride (43 g) was injected, and a solution of an azo group-containingwater-soluble initiator (0.86 g) in water (9 g) was added to conduct areaction at 60° C. for 5 hours, whereby obtaining an aqueous dispersionof polymer. The composition of the polymer was almost the same as theformulations of charged monomers.

Preparative Example 2

CF₃CF₂—(CF₂CF₂)_(n)—CH₂CH₂OCOC(Cl)═CH₂ (n=2.0) (97.2 g), butyl acrylate(73.66 g), pure water (405 g), aqueous glycol solvent (34.8 g),alkylamine oxide (11.75 g), and polyoxyethylene alkyl ether (6.17 g)were charged into a 1000 mL autoclave, and ultrasonicallyemulsification-dispersed at 60° C. for 15 minutes with stirring. Afterthe atmosphere in the autoclave was replaced with nitrogen, vinylchloride (43 g) was injected, and a solution of an azo group-containingwater-soluble initiator (0.86 g) in water (9 g) was added to conduct areaction at 60° C. for 5 hours, whereby obtaining an aqueous dispersionof polymer. The composition of the polymer was almost the same as theformulations of charged monomers.

Preparative Example 3

CF₃CF₂—(CF₂CF₂)_(n)—CH₂CH₂OCOC(Cl)═CH₂ (n=2.0) (97.2 g), lauryl acrylate(49.1 g), isobornyl methacrylate (24.5 g), pure water (405 g), aqueousglycol solvent (34.8 g), alkylamine oxide (11.75 g), and polyoxyethylenealkyl ether (6.17 g) were charged into a 1000 mL autoclave, andultrasonically emulsification-dispersed at 60° C. for 15 minutes withstirring. After the atmosphere in the autoclave was replaced withnitrogen, vinyl chloride (43 g) was injected, and a solution of an azogroup-containing water-soluble initiator (0.86 g) in water (9 g) wasadded to conduct a reaction at 60° C. for 5 hours, whereby obtaining anaqueous dispersion of polymer. The composition of the polymer was almostthe same as the formulations of charged monomers.

Comparative Preparative Example 1

CF₃CF₂—(CF₂CF₂)_(n)—CH₂CH₂OCOC(CH₃)═CH₂ (n=2.0) (133 g), lauryl acrylate(37.6 g), pure water (405 g), aqueous glycol solvent (34.8 g),alkylamine oxide (11.75 g), and polyoxyethylene alkyl ether (6.17 g)were charged into a 1000 mL autoclave, and ultrasonicallyemulsification-dispersed at 60° C. for 15 minutes with stirring. Afterthe atmosphere in the autoclave was replaced with nitrogen, vinylchloride (43 g) was injected, and a solution of an azo group-containingwater-soluble initiator (0.86 g) in water (9 g) was added to conduct areaction at 60° C. for 5 hours, whereby obtaining an aqueous dispersionof polymer. The composition of the polymer was almost the same as theformulations of charged monomers.

Comparative Preparative Example 2

CF₃CF₂—(CF₂CF₂)_(n)—CH₂CH₂OCOC(Cl)═CH₂ (n=2.0) (97.2 g), stearylacrylate (73.66 g), pure water (405 g), aqueous glycol solvent (34.8 g),alkylamine oxide (11.75 g), and polyoxyethylene alkyl ether (6.17 g)were charged into a 1000 mL autoclave, and ultrasonicallyemulsification-dispersed at 60° C. for 15 minutes with stirring. Afterthe atmosphere in the autoclave was replaced with nitrogen, vinylchloride (43 g) was injected, and a solution of an azo group-containingwater-soluble initiator (0.86 g) in water (9 g) was added to conduct areaction at 60° C. for 5 hours, whereby obtaining an aqueous dispersionof polymer. The composition of the polymer was almost the same as theformulations of charged monomers.

Example 1

After diluting the aqueous dispersion produced in Preparative Example 1with pure water to give a fluorine-containing polymer solidconcentration of 30%, 1.8 g of the 30% diluted liquid and 0.20 g of acrosslinking agent (a blocked isocyanate) were diluted with pure waterto prepare 100 g of a test liquid. Four sheets of wood pulp/polyesternonwoven fabric (510 mm×205 mm, 30/70 of wood pulp/polyester weightratio) were dipped in this test liquid, passed through a mangle, driedat 100° C. for 30 seconds, and treated by a pin tenter at 170° C. for 2minutes. Then, a shower water repellency test, a water repellency test,a water pressure resistance test, an IPR test, and a tensile strengthtest were conducted for the test fabrics. Results are shown in Table 3.

Examples 2 to 4 and Comparative Examples 1 to 2

The polymers produced in Preparative Examples 2-4 and ComparativePreparative Examples 1-2 were used for the treatment as in Example 1,and the shower water repellency test, the water repellency test, thewater pressure resistance test, the IPR test, and the tensile strengthtest were conducted. Results are shown in Table 3.

The meanings of abbreviations in the Tables are as follows:

Abbreviation Compound name/Chemical formula C6SFCIAC₆F₁₃CH₂CH₂OCOC(Cl)═CH₂ C6SFMA C₆F₁₃CH₂CH₂OCOC(CH₃)═CH₂ LA Laurylacrylate BA Butyl acrylate StA Stearyl acrylate VCM Vinyl chloride IBMAIsobornyl methacrylate

TABLE 3 Com. Ex. Ex. Com. Com. Pre. Pre. Pre. Pre. Pre. Ex. 1 Ex. 2 Ex.3 Ex. 1 Ex. 2 Polymer C6SFCIA 50 50 50 50 components C6SFMA 70 VCM 20 2020 20 20 LA 30 20 10 BA 30 StA 30 IBMA 10 Treatment Sample g/20% 1.8%1.8% 1.8% 1.8% 1.8% recipe solid content Cross linking 0.2% 0.2% 0.2%0.2% 0.2% agent (blocked isocyanate) Wood pulp/ IPA % 90 90 90 80 90polyester Spray 90 90 90 70 80 nonwoven IPR g 0.22 0.41 0.21 0.65 0.22fabric Hydro Head mbar 21.3 21.4 20.4 21.7 21.5 Wet pick up 110% TensileLengthwise N 241 233 211 194 192 strength direction (MD) Transverse N 4338 36 35 30 direction (CD)

INDUSTRIAL APPLICABILITY

The nonwoven fabric of the present invention can be used in, forexample, a medical use, an industrial material use, a civil engineeringand construction use, and an agricultural and horticultural use.Specific uses include a surgical cloth, a package cloth, a bedsheet, apillow case, a disposable diaper and a sanitary napkin.

Embodiments of the present invention are as follows:

1) A nonwoven fabric to which a fluorine-containing polymer is adhered,wherein the fluorine-containing polymer comprises:(a) repeating units derived from a fluorine-containing monomer which isalpha-chloro acrylate or alpha-chloro acrylamide having a fluoroalkylgroup, and(b) repeating units derived from a halogenated olefin monomer, and thefluorine-containing polymer is free from repeating unit derived from a(meth)acrylate containing a linear or branched hydrocarbon group havingat least 18 carbon atoms.2) The nonwoven fabric according to any embodiment above, wherein thefluorine-containing monomer (a) is a compound represented by theformula:

CH2═C(—Cl)—C(═O)—Y—Z—Rf

wherein Y is —O— or —NH—;Z is a direct bond or divalent organic group; andRf is a fluoroalkyl group having 1 to 20 carbon atoms.3) The nonwoven fabric according to any embodiment above, wherein thehalogenated olefin is an olefin having 2-20 carbon atoms substituted by1-10 chlorine atoms, bromine atoms or iodine atoms.4) The nonwoven fabric according to any embodiment above, wherein thefluorine-containing polymer further comprises:(c) repeating unit derived from a (meth)acrylate containing a linear orbranched hydrocarbon group having 17 or less carbon atoms.5) The nonwoven fabric according to any embodiment above, wherein thefluorine-containing polymer further comprises at least one selected fromthe group consisting of:(d) repeating units derived from a (meth)acrylate or (meth)acrylamidemonomer having a cyclic hydrocarbon group, and(e) repeating units derived from a fluorine-free crosslinking(meth)acrylate or (meth)acrylamide monomer.6) The nonwoven fabric according to any embodiment above, wherein thesubstrate is a combination of cellulosic fibers and polyester fibers.7) The nonwoven fabric according to any embodiment above, wherein theamount of the fluorine-containing monomer (a) is 20% to 90% by weight,based on the fluorine-containing polymer, andthe amount of the halogenated olefin monomer (b) is 5 to 300 parts byweight, based on 100 parts by weight of the fluorine-containing monomer(a).8) The nonwoven fabric according to any embodiment above, wherein theamount of the fluorine-containing polymer adhering to the nonwovenfabric substrate is 0.01 to 5 parts by weight, based on 100 parts byweight of nonwoven fabric substrate.9) A method of producing the nonwoven fabric according to any embodimentabove, which comprises applying the fluorine-containing polymer to thesubstrate.

1. A nonwoven fabric comprising (i) a nonwoven fabric substrate and (ii)a fluorine-containing polymer adhering to the nonwoven fabric substrate,wherein the fluorine-containing polymer comprises: (a) repeating unitsformed from a fluorine-containing monomer which is alpha-chloro acrylateor alpha-chloro acrylamide containing a fluoroalkyl group, and (b)repeating units formed from a halogenated olefin monomer, and thefluorine-containing polymer is free from repeating units formed from a(meth)acrylate containing a linear or branched hydrocarbon group havingat least 18 carbon atoms.
 2. The nonwoven fabric according to claim 1,wherein the fluorine-containing monomer (a) is a compound represented bythe formula:CH₂═C(—Cl)—C(═O)—Y—Z—Rf wherein Y is —O— or —NH—; Z is a direct bond ordivalent organic group; and Rf is a fluoroalkyl group having 1 to 20carbon atoms.
 3. The nonwoven fabric according to claim 1, wherein Z isa direct bond, a linear or branched aliphatic group having 1-20 carbonatoms, an aromatic group or cycloaliphatic group having 6-18 carbonatoms, a group represented by the formula —R²(R¹)N—SO₂— or the formula—R²(R¹)N—CO— wherein R¹ is an alkyl group having 1 to 10 carbon atomsand R² is a linear alkylene group or branched alkylene group having 1 to10 carbon atoms, for example, by a —CH₂CH₂N(R¹)SO₂— group wherein R¹ isan alkyl group having 1 to 4 carbon atoms, a group represented by theformula —CH₂CH(OR³)CH₂—[Ar—(O)_(q)]_(p)— wherein R³ is a hydrogen atomor an acyl group having 1 to 10 carbon atoms, Ar is an arylene groupoptionally having a substituent group, p is 0 or 1, and q is 0 or 1, agroup represented by the formula —(CH₂)_(n)—Ar—(O)_(q)— (wherein Ar isan arylene group optionally having a substituent group, n is 0-10, and qis 0 or 1), or a —(CH₂)_(m)—SO₂—(CH₂)_(n)— group or a—(CH₂)_(m)—S—(CH₂)_(n)— group wherein m is 1-10, and n is 0-10.
 4. Thenonwoven fabric according to claim 1, wherein the halogenated olefinmonomer (b) is an olefin having 2-20 carbon atoms and substituted by1-10 chlorine atoms, bromine atoms or iodine atoms.
 5. The nonwovenfabric according to claim 4, wherein the halogenated olefin monomer (b)is at least one selected from the group consisting of vinyl chloride andvinylidene chloride.
 6. The nonwoven fabric according to claim 1,wherein the fluorine-containing polymer further comprises afluorine-free non-crosslinkable monomer, and the fluorine-freenon-crosslinkable monomer is at least one selected from the groupconsisting of: (c1-i) repeating units formed from a (meth)acrylate or(meth)acrylamide monomer containing a linear or branched hydrocarbongroup having 17 or less carbon atoms, and (c1-ii) repeating units formedfrom a (meth)acrylate or (meth)acrylamide monomer containing a cyclichydrocarbon group.
 7. The nonwoven fabric according to claim 6, whereinthe (meth)acrylate or (meth)acrylamide monomers (c1-i) and (c1-ii) are acompound represented by the formula:CH₂═CA-T wherein A is a hydrogen atom, a methyl group, or a halogen atomother than a fluorine atom, T is an open-chain or cyclic organic grouphaving 1 to 31 carbon atoms and an ester bond or amide bond.
 8. Thenonwoven fabric according to claim 6, wherein the (meth)acrylate or(meth)acrylamide monomer containing a linear or branched hydrocarbongroup having 17 or less carbon atoms (c1-i) is an acrylate representedby the formula:CH₂═CA¹CO—Z¹-A² wherein A¹ is a hydrogen atom, a methyl group, or ahalogen atom other than a fluorine atom, Z¹ is —O— or —NH—, and A² is analkyl group represented by C_(n)H_(2n+1) wherein n is 1 to
 17. 9. Thenonwoven fabric according to claim 1, wherein the fluorine-containingpolymer further comprises: (c2) repeating units formed from afluorine-free crosslinking (meth)acrylate or (meth)acrylamide monomer.10. The nonwoven fabric according to claim 1, wherein the nonwovenfabric substrate is a combination of natural fibers and syntheticfibers,
 11. The nonwoven fabric according to claim 10, wherein thenonwoven fabric substrate is a combination of cellulosic fibers andpolyester fibers.
 12. The nonwoven fabric according to claim 10, whereinthe weight ratio of the natural fiber to the synthetic fiber is15:85-45:55.
 13. The nonwoven fabric according to claim 1, wherein theamount of the fluorine-containing monomer (a) is 20% to 90% by weight,based on the fluorine-containing polymer, and the amount of thehalogenated olefin monomer (b) is 5 to 300 parts by weight, based on 100parts by weight of the fluorine-containing monomer (a).
 14. The nonwovenfabric according to claim 6, wherein the amount of each of thefluorine-free non-crosslinkable monomers (c1-i) and (c1-ii) is 0 to 500parts by weight, based on 100 parts by weight of the fluorine-containingmonomer (a).
 15. The nonwoven fabric according to claim 1, wherein theamount of the fluorine-containing polymer adhering to the nonwovenfabric substrate is 0.01 to 5 parts by weight, based on 100 parts byweight of the nonwoven fabric substrate.
 16. A method of producing thenonwoven fabric according to claim 1, which comprises applying thefluorine-containing polymer to the nonwoven fabric substrate.
 17. Themethod according to claim 16, wherein the fluorine-containing polymer isin the form of an aqueous dispersion.